Construction of supramolecular S-scheme heterojunctions assisted by hydrogen bond subtle-tuning actuates highly efficient photocatalytic oxidation

[Display omitted] •S-scheme hydrogen-bonded SubPc-2/Ag3PO4 heterojunction was successfully fabricated.•SubPc-2/Ag3PO4 exhibits efficient and stable photocatalytic degradation of PPCPs.•Theoretical and experimental results prove the S-scheme electron transport mechanism.•Photodegradation pathways were proposed based on DFT and HPLC-MS results. Controllable fine-tuning of heterojunction interfaces at the atomic level represents a promising strategy for enhancing semiconductor photocatalytic performance. Herien, we propose a strategy to introduce hydrogen-bonded electron channels at the heterojunction interface to achieve rapid interfacial electron transfer. This S-scheme hydrogen-bonded supramolecular self-assembled H12SubPcB-OPhCH2COOH/Ag3PO4 semiconductor heterojunction exhibits efficient and stable photocatalytic degradation of a wide range of pharmaceuticals and personal care products. Experimental results and theoretical simulations demonstrate that the interface O-H⋅⋅⋅O hydrogen bond at the heterojunction generates an internal electric field, which provides the driving force for accelerated S-scheme charge transfer and enhanced redox properties. Furthermore, the combination of TDDFT calculations and synchronous illumination XPS has revealed that hydrogen bonding acts as a suction electron pump in the excited state, transferring electrons from Ag3PO4 to SubPc-2. These findings suggest that hydrogen-bonded supramolecular semiconductor can be used to develop high-performance photocatalytic materials for environmental remediation.